JP2005029609A - Resin composition - Google Patents
Resin composition Download PDFInfo
- Publication number
- JP2005029609A JP2005029609A JP2003193491A JP2003193491A JP2005029609A JP 2005029609 A JP2005029609 A JP 2005029609A JP 2003193491 A JP2003193491 A JP 2003193491A JP 2003193491 A JP2003193491 A JP 2003193491A JP 2005029609 A JP2005029609 A JP 2005029609A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- weight
- diene polymer
- modified
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 45
- 229920000642 polymer Polymers 0.000 claims abstract description 61
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 22
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 22
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 41
- 150000001993 dienes Chemical class 0.000 claims description 37
- 125000000524 functional group Chemical group 0.000 claims description 19
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- -1 nitrogen-containing compound Chemical class 0.000 claims description 10
- 125000003700 epoxy group Chemical group 0.000 claims description 9
- 238000005187 foaming Methods 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000002210 silicon-based material Substances 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000005372 silanol group Chemical group 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 13
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 20
- 229920001971 elastomer Polymers 0.000 description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 18
- 239000005060 rubber Substances 0.000 description 18
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 229920002857 polybutadiene Polymers 0.000 description 11
- 239000005062 Polybutadiene Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000004088 foaming agent Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 239000003431 cross linking reagent Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 150000001934 cyclohexanes Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 229920006168 hydrated nitrile rubber Polymers 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000013585 weight reducing agent Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000944 linseed oil Substances 0.000 description 2
- 235000021388 linseed oil Nutrition 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000011191 terminal modification Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- 229960002447 thiram Drugs 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- OPNUROKCUBTKLF-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N\C(N)=N\C1=CC=CC=C1C OPNUROKCUBTKLF-UHFFFAOYSA-N 0.000 description 1
- HIACAHMKXQESOV-UHFFFAOYSA-N 1,2-bis(prop-1-en-2-yl)benzene Chemical compound CC(=C)C1=CC=CC=C1C(C)=C HIACAHMKXQESOV-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- UJPKMTDFFUTLGM-UHFFFAOYSA-N 1-aminoethanol Chemical compound CC(N)O UJPKMTDFFUTLGM-UHFFFAOYSA-N 0.000 description 1
- JPOUDZAPLMMUES-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)octane Chemical compound CCCCCCC(C)(OOC(C)(C)C)OOC(C)(C)C JPOUDZAPLMMUES-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- GUKQCRBUPPCDSA-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]propan-2-ylbenzene Chemical compound CC(C)(C)OC(C)(C)C1=CC=CC=C1 GUKQCRBUPPCDSA-UHFFFAOYSA-N 0.000 description 1
- PFJPHQUZCRACDD-UHFFFAOYSA-N 2-[[4-(oxiran-2-ylmethyl)phenyl]methyl]oxirane Chemical compound C=1C=C(CC2OC2)C=CC=1CC1CO1 PFJPHQUZCRACDD-UHFFFAOYSA-N 0.000 description 1
- YRVRZDIWEXCJSX-UHFFFAOYSA-N 2-methyl-3-(3-triethoxysilylpropyl)thiirane-2-carboxylic acid Chemical compound CCO[Si](OCC)(OCC)CCCC1SC1(C)C(O)=O YRVRZDIWEXCJSX-UHFFFAOYSA-N 0.000 description 1
- OVEUFHOBGCSKSH-UHFFFAOYSA-N 2-methyl-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound CC1=CC=CC=C1N(CC1OC1)CC1OC1 OVEUFHOBGCSKSH-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- CPGFMWPQXUXQRX-UHFFFAOYSA-N 3-amino-3-(4-fluorophenyl)propanoic acid Chemical compound OC(=O)CC(N)C1=CC=C(F)C=C1 CPGFMWPQXUXQRX-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- SRGBNANKQPZXFZ-UHFFFAOYSA-N aniline;butanal Chemical compound CCCC=O.NC1=CC=CC=C1 SRGBNANKQPZXFZ-UHFFFAOYSA-N 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- VJRITMATACIYAF-UHFFFAOYSA-N benzenesulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=CC=C1 VJRITMATACIYAF-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- VTEKOFXDMRILGB-UHFFFAOYSA-N bis(2-ethylhexyl)carbamothioylsulfanyl n,n-bis(2-ethylhexyl)carbamodithioate Chemical compound CCCCC(CC)CN(CC(CC)CCCC)C(=S)SSC(=S)N(CC(CC)CCCC)CC(CC)CCCC VTEKOFXDMRILGB-UHFFFAOYSA-N 0.000 description 1
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 description 1
- RTACIUYXLGWTAE-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene;styrene Chemical compound C=CC=C.CC(=C)C=C.C=CC1=CC=CC=C1 RTACIUYXLGWTAE-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 150000001717 carbocyclic compounds Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- OYOFUEDXAMRQBB-UHFFFAOYSA-N cyclohexylmethanediamine Chemical compound NC(N)C1CCCCC1 OYOFUEDXAMRQBB-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- LIQOCGKQCFXKLF-UHFFFAOYSA-N dibromo(dimethyl)silane Chemical compound C[Si](C)(Br)Br LIQOCGKQCFXKLF-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- NJVOZLGKTAPUTQ-UHFFFAOYSA-M fentin chloride Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 NJVOZLGKTAPUTQ-UHFFFAOYSA-M 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- PPMXDDJEXJDFMT-UHFFFAOYSA-N n,n-diethyl-3-phenylprop-2-en-1-amine Chemical compound CCN(CC)CC=CC1=CC=CC=C1 PPMXDDJEXJDFMT-UHFFFAOYSA-N 0.000 description 1
- SYUYXOYNRMMOGW-UHFFFAOYSA-N n,n-dimethyl-3-phenylprop-2-en-1-amine Chemical compound CN(C)CC=CC1=CC=CC=C1 SYUYXOYNRMMOGW-UHFFFAOYSA-N 0.000 description 1
- UBHHTPOLMACCDD-UHFFFAOYSA-N n,n-dimethyl-4-phenylbut-3-en-1-amine Chemical compound CN(C)CCC=CC1=CC=CC=C1 UBHHTPOLMACCDD-UHFFFAOYSA-N 0.000 description 1
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229910000489 osmium tetroxide Inorganic materials 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- DWAWYEUJUWLESO-UHFFFAOYSA-N trichloromethylsilane Chemical compound [SiH3]C(Cl)(Cl)Cl DWAWYEUJUWLESO-UHFFFAOYSA-N 0.000 description 1
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、光沢を抑え艶消し効果が優れる樹脂組成物及びその発泡体と、該樹脂組成物を使用した履物に関するものである。
【０００２】
【従来の技術】
従来、靴用途などでの軽量発泡靴底は軽量化目的の発泡性、ゴム弾性、柔軟性、低温特性等の特徴を有するエチレン酢酸ビニルコポリマー（以下、ＥＶＡと略することもある）が多く使用されている。しかし、ＥＶＡ発泡体は光沢度が大きいために好ましくない艶があり質感が乏しい。
この問題を解決するために、コンプレッションモールドで発泡シートを製造した後、型取りしているが材料のロス率が非常に大きい。またインジェクションモールドでの発泡成形は、ストーンウオッシュなどの艶消し処方が必要とされているが、材料のロスや環境対策など種々問題の解決が望まれている。
更に、発泡成形品の加熱収縮性などが大きく２次加硫の障害となっている。
【０００３】
特許文献１にはＥＶＡと水素添加アクリロニトリルブタジエンゴム（ＨＮＢＲ）からなる発泡組成物が記載されており、ＥＶＡの耐摩耗性とＨＮＢＲの硬度を改良することが開示されている。
特許文献２にはスチレン−ブタジエンブロック共重合体とＥＶＡ、またはスチレン−ブタジエンブロック共重合体とポリウレタン（ＰＵ）の発泡組成物が温度による硬度変化の小さいことが開示されている。
【０００４】
【特許文献１】
特開２００２−３４６０１号公報
【特許文献２】
特開２００１−３４０１０５号公報
【０００５】
【発明が解決しようとする課題】
本発明は光沢度を抑え艶消し効果が極めて大きく、かつ熱収縮性や機械的強度が優れる樹脂組成物と、その樹脂組成物を使用した、優れた質感を有する履物を提供することを目的とする。
【０００６】
【課題を解決するための手段】
本発明は、前記課題を解決するために特定のジエン系重合体とＥＶＡからなる樹脂組成物が、光沢度を抑え艶消し効果が極めて大きく、かつ熱収縮性や機械的強度が優れることを見出してなされたものである。
【０００７】
即ち、本発明は
（１）官能基で変性された分子量１００，０００〜１，２００，０００のジエン系重合体２〜５０重量部と酢酸ビニル含有量６〜４５重量％のエチレン酢酸ビニルコポリマー（ＥＶＡ）９８〜５０重量部からなる樹脂組成物、
（２）ジエン系重合体のビニル芳香族結合量が、２５〜７５重量％である上記（１）記載の樹脂組成物、
（３）ジエン系重合体のビニル芳香族ブロック結合量が、１８重量％以下である上記（１）及び（２）記載の樹脂組成物、
【０００８】
（４）ジエン系重合体が、含窒素化合物、含酸素化合物、含珪素化合物、含錫化合物から選ばれる少なくとも１種以上の化合物で変性された官能基変性ジエン系重合体である上記（１）から（３）のいずれかに記載の樹脂組成物、
（５）ジエン系重合体がアミノ基、アミド基、イミノ基、エポキシ基、シラノール基のうち１種以上を有する化合物で変性された官能基変性ジエン系重合体である上記（１）から（４）のいずれかに記載の樹脂組成物、
（６）ジエン系重合体が、下記式（１）で示される化合物で変性された官能基変性ジエン系重合体である（１）から（５）のいずれかに記載の樹脂組成物、
【０００９】
【化２】
（７）上記（１）から（６）のいずれかに記載の樹脂組成物を使用した発泡弾性体、
（８）上記（１）〜（６）のいずれかに記載の樹脂組成物または上記（７）に記載の発泡弾性体を使用した履物、
である。
【００１１】
【発明の実施の形態】
本発明は、官能基で変性された分子量１００，０００〜１，２００，０００のジエン系重合体２〜５０重量部と酢酸ビニル含有量６〜４５重量％のエチレン酢酸ビニルコポリマー（ＥＶＡ）９８〜５０重量部からなる樹脂組成物であって、特に該樹脂組成物の光沢度が抑えられた好ましい質感を有し、加熱収縮性が優れる樹脂組成物である。
【００１２】
本発明で用いられる官能基で変性されたジエン系重合体はゲルパーミエーションクロマトグラフィー（以下、ＧＰＣと記する）で測定するポリスチレン換算の主ピーク分子量（クロマトグラムが複数のピークを有する場合、ピーク高さが最も高い部分の分子量を表す）が１００，０００〜１，２００，０００、好ましくは３００，０００〜１，１００，０００、より好ましくは４００，０００〜１，０００，０００である。この分子量範囲で優れた艶消し効果を有する樹脂組成物が得られる。
【００１３】
本発明で用いられる官能基で変性されたジエン系重合体は分子内に各種官能基を有する重合体である。
分子内に各種官能基を有するジエン系重合体としては、例えばポリブタジエンゴム（ＢＲ）、スチレン・ブタジエンゴム（ＳＢＲ）、ポリイソプレンゴム（ＩＲ）、スチレン・イソプレン・ブタジエンゴム（ＳＩＢＲ）、ニトリル・ブタジエンゴム（ＮＢＲ）更には高純度天然ゴム（ＮＲ）などの変性ゴムである。
【００１４】
官能基変性ジエン重合体中における官能基付加位置は分子末端変性、分子両末端（頭尾）変性、カップリング変性、主鎖変性などが含まれる。分子末端変性を行う方法としては、例えば重合分子活性末端を官能基含有化合物で変性する方法が挙げられる。
両末端変性は例えばアニオン重合の触媒に多官能開始剤を使用して該重合体活性末端を変性する方法や、官能基を有する開始剤を使用し該重合体活性末端を変性する又は方法や官能基含有単量体を重合原料として該重合体活性末端を変性する方法、又は官能基含有重合体活性末端をカップリング剤でカップリングする方法などである。また、該重合体の活性末端を多官能変性剤で処理することにより、カップリング変性した重合体も好ましいジエン系重合体として使用できる。
【００１５】
官能基変性ジエン系重合体は本発明の樹脂組成物１００重量部中、２〜５０重量部、好ましくは３〜４０重量部であることにより艶消し効果が大きく、加硫後の加熱収縮性が小さい耐熱収縮性の優れた樹脂組成物が得られる。
本発明組成物の好ましい官能基変性ジエン系重合体はビニル芳香族結合量が２５〜７５重量％、特に好ましくは３０〜７０重量％であり、この範囲で好ましい耐熱収縮性の樹脂組成物が得られる。
また、本発明組成物の官能基変性ジエン系重合体はビニル芳香族ブロックの結合量が該重合体１８重量％以下であり、ビニル芳香族の結合がよりランダムであることが望ましい。ビニル芳香族の結合がよりランダムであることにより、好ましい艶消し効果と耐圧縮永久歪性が得られる。
【００１６】
本発明の特に好ましい官能基変性ジエン系重合体は官能基変性スチレン・ブタジエンゴムである。
本発明で用いられる官能基変性スチレン・ブタジエンゴムの好ましい結合スチレン量は２５〜７５重量％、特に好ましくは３０〜７０重量％である。この結合スチレン量の範囲でより好ましい艶消し効果が得られる。
【００１７】
官能基変性スチレン・ブタジエンゴムの分子内におけるスチレンの分布はランダム分布の方がより艶消し効果は高い。官能基変性ポリブタジエンゴムや官能基変性スチレン・ブタジエンゴムにおけるブタジエン部分のビニル結合量は特に制限は無いが、靴底などに使用する場合は耐摩耗性などを考慮すると８０重量％以下が望ましい。
本発明ゴム組成物の官能基変性率は高い方がその艶消し効果と物性のバランスは良好であり、全ゴム分子のうち１個以上の官能基が付加している変性ゴムの割合（変性率）は２０重量％以上、好ましくは４０重量％以上である。
【００１８】
本発明ゴム組成物の官能基変性ゴム状重合体の変性剤化合物としては、好ましくは含窒素化合物、含酸素化合物、含珪素化合物、含錫化合物のうち１種以上である。含窒素化合物としては、例えばアミノ基、アミド基、イミノ基などを有する化合物であり、例えばジメチルアミン、メチルエチルアミン、ジエチルアミン、ジフェニルアミン、Ｎ−メチルアニリンなどであり、Ｎ−アルキル環状ラクタム化合物、Ｎ−アルキル環状尿素化合物又はＮ−アルキルベンゾフェノン化合物なども好ましい官能基含有化合物であり、具体的な化合物としては、例えばＮ−メチル−２−ピロリドン、１，３−ジメチル−２−イミダゾリジノン、Ｎ，Ｎ′−ジメチルベンゾフェノンなどである。
【００１９】
含酸素化合物としては例えばエポキシ基、カルボキシル基、水酸基などであり、特に好ましいのはエポキシ基を含有する化合物である。エポキシ基を有する化合物としては、例えばエポキシ化大豆油、エポキシ化亜麻仁油、エポキシ化ポリブタジエンなどであり、グリシジル基を有する化合物も好適である。
特に好ましいエポキシ基含有化合物としては例えば、下記式（１）で表されるジグリシジル化合物である。
【００２０】
【化３】
式（１）で表される具体的な化合物としては、例えばエチレングリコールジグリシジルエーテル等の多価アルコールのポリグリシジルエーテル、１，４−ジグリシジルベンゼン、ポリエポキシ化液状ポリブタジエン等のポリエポキシ化合物、４，４’−ジグリシジル−ジフェニルメチルアミン、４，４’−ジグリシジル−ジベンジルメチルアミン等のエポキシ基含有３級アミン、ジグリシジルアニリン、ジグリシジルオルソトルイジン、テトラグリシジルメタキシレンジアミン、ジグリシジルアミノメチルシクロヘキサン、テトラグリシジル−１，３−ビスアミノメチルシクロヘキサン等のジグリシジルアミノ化合物があげられる。
エポキシ基含有化合物としては例えば、下記式（２）で表される化合物なども好ましい化合物である。
【００２２】
【化４】
式（２）中のＲは、式（３）〜（５）で表すジエポキシ化合物である。
【００２４】
【化５】
【化６】
または
【００２７】
【化７】
具体例としては式（６）または（７）で示されるビスフェノールＡジグリシジルエーテルや、ビスフェノールＦジグリシジルエーテルなどであり、その他アルキレンオキシド含有エポキシ化合物、脂環式エポキシ化合物、炭素環化合物含有エポキシ化合物などであって、これら式（２）で表される化合物の混合物も使用できる。
【００２９】
【化８】
【化９】
（式中、ｎは０〜１０の整数を示す）
【００３２】
含珪素化合物としては例えばハロゲンやアルコキシ基などを有する化合物であり、例えば四塩化珪素、トリクロロメチルシラン、ジクロロジメチルシラン、トリメチルクロロシラン、テトラメトキシシラン、テトラエトキシシラン、ジブロモジメチルシランなどである。
含錫化合物としてはハロゲン化錫などであり、例えば四塩化錫、二塩化錫、トリフェニル錫クロリド、トリブチル錫クロリドなどである。
【００３３】
また、両末端変性ジエン系重合体は例えば有機リチウム化合物などの有機アルカリ金属を、例えばジビニルベンゼンやジイソプロペニルベンゼンなどのポリビニル化合物で変性したポリリチウム化合物を重合開始剤として、得られた重合体の活性末端を官能基含有化合物で変性する方法である。また、例えばアミドリチウム化合物などの官能基含有重合開始剤を使用して得られた重合体の活性末端をカップリング剤でカップリングする方法や官能基含有化合物で変性する方法である。更に、例えばＮ，Ｎ−ジメチルアミノメチルスチレン、Ｎ，Ｎ−ジエチルアミノメチルスチレン、Ｎ，Ｎ−ジメチルアミノエチルスチレンなどのアミノ基含有化合物のような官能基含有単量体を重合原料として得られた重合体の活性末端を変性する方法やカップリングする方法などである。
【００３４】
このような官能基含有変性剤を２種以上併用することも可能であり、その他の変性剤を使用する事も可能である。変性剤とカップリング剤を併用することも出来る。本発明で使用する官能基変性ジエン系重合体はその構造がリニア−構造でも良く、分岐構造でも良い。
本発明で用いられる官能基変性ジエン系重合体は、透明品やカラー用途などに使用する場合は着色性が優れる不純物が少ない溶液重合ゴムが望ましい。
【００３５】
本発明で使用するエチレン−酢酸ビニル共重合体（ＥＶＡ）としては酢酸ビニル含有量によって種々の市販品があるが酢酸ビニル含有量６〜４５重量％のものが使用できる。好ましい酢酸ビニル含有量の範囲は８〜４０重量％である。この範囲で良好な加工性を有し、官能基変性ジエン系重合体を配合することにより艶消し効果と物性バランスが良好となる。
【００３６】
本発明は分子量１００，０００〜１，２００，０００のジエン系重合体２〜５０重量部と酢酸ビニル含有量６〜４５重量％のエチレン酢酸ビニルコポリマー（ＥＶＡ）９８〜５０重量部からなる樹脂組成物であるが、その他に発泡剤、架橋剤、各種添加剤からなるものである。また、その他の重合体類が必要に応じＥＶＡの５０重量％以下混合されるものでも良い。
その他のジエン系重合体類としては、例えば天然ゴム（ＮＲ）、ポリイソプレンゴム（ＩＲ）、ポリブタジエンゴム（ＢＲ）、スチレン・ブタジエンゴム（ＳＢＲ）、アクリロニトリルゴム（ＮＢＲ）、エチレン・プロピレンゴム（ＥＰＭ又はＥＰＤＭ）などが挙げられる。
【００３７】
本発明で用いられる発泡剤としては公知のものが使用される。例えば炭酸ナトリウム、炭酸アンモニウム、重炭酸ナトリウム、重炭酸アンモニウム、アゾジカルボンアミド、Ｎ，Ｎ′−ジニトロソペンタメチレンテトラミン、アゾビスイソブチロニトリル、ベンゼンスルホニルヒドラジドなど１種以上が使用できる。発泡剤の使用量は、樹脂組成物１００重量部当たり１〜２５重量部、好ましくは２〜２０重量部であり、この範囲で樹脂組成物を靴底などに使用する場合の好ましい軽量化と強度などの性能バランスが得られる。発泡による軽量化の好ましい比重は０．１〜０．９、より好ましくは０．１５〜０．７である。
また、発泡剤と共にサリチル酸などの有機酸や尿素または尿素誘導体類を発泡助剤として使用できる。
【００３８】
本発明の発泡弾性体の架橋方法は公知の各種方法が採用できるが、架橋剤を使用する場合は、例えば有機過酸化物や硫黄系の架橋剤・加硫剤が使用できる。有機過酸化物としては例えばジクミルパーオキシド、１，１−ビス（ｔ−ブチルパーオキシ）３，３，５−トリメチルシクロヘキサン、シクロヘキサンパーオキシド、ｔ−ブチルパーオキシベンゾエート、ｔ−ブチルクミルオキシド、ベンゾイルパーオキシド、１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサン、２，２−ビス（ｔ−ブチルパーオキシ）オクタン、ジ−ｔ−ブチルパーオキシドなどが挙げられる。
【００３９】
また、硫黄系の加硫剤としては硫黄または各種処理硫黄や硫黄誘導体が使用できる。例えば４−４′−ジチオジモルホリンなどである。その他ｐ−キノンジオキシム、ｐ−ｐ′−ジベンゾイルキノンジオキシム、Ｎ，Ｎ′−ｍ−フェニレンジマレイミドなども使用できる。このような加硫剤を使用する場合は加硫促進剤を併用することが有効である。
【００４０】
加硫促進剤としては、例えばアルデヒドアンモニア系、アルデヒドアミン系、チオウレア系、グアニジン系、チアゾール系、アルデヒドアミン系、スルフェンアミド系、チウラム系、ジチオカルバミン酸塩系などであり、具体的には例えばヘキサメチレンテトラミン、ｎ−ブチルアルデヒドアニリン、Ｎ，Ｎ′−ジフェニルチオ尿素、１，３−ジフェニルグアニジン、ジ−ｏ−トリルグアニジン、２−メルカプトベンゾチアゾール、ジベンゾチアゾリルジスルフィド、ｎ−シクロヘキシル−２−ベンゾチアゾリルスルフェンアミド、Ｎ−ｔｅｒｔ−ブチル−２−ベンゾチアゾリルスルフェンアミド、テトラメチルチウラムジスルフィド、テトラキス（２−エチルヘキシル）チウラムジスルフィド、ジペンタメチレンチウラムテトラスルフィド、ジメチルジチオカルバミン酸亜鉛などである。
【００４１】
本発明の樹脂組成物は本発明の目的に沿う範囲で、軟化剤として各種のゴム用伸展油を全重合体１００重量部当たり０〜１００重量部添加しても良い。
添加できるオイルとしては、例えばアロマ−系オイル、パラフィン系オイル、ナフテニック系オイルなどの鉱物油や大豆油、亜麻仁油などの動植物系オイルなどであり、これらの２種以上の混合物でも良い。好ましい伸展油は樹脂組成物の着色性などを考慮する場合、非汚染性の鉱物油であり、例えばナフテニックオイルやパラフィンオイルなどである。
【００４２】
本発明樹脂組成物は必要に応じ各種の充填剤を使用することができる。一般的に樹脂やゴムの充填剤として公知のものであり、例えばカーボンブラック、シリカ、亜鉛華、炭酸亜鉛、炭酸カルシウム、炭酸マグネシウム、水酸化マグネシウム、炭酸カルシウム、炭酸マグネシウム、クレー、タルク、マイカなどであり、好ましいのはハードクレー、炭酸カルシウム、シリカなどであり２種以上を併用することも出来る。充填剤としては、補強性効果のあるものが望ましい。
【００４３】
充填剤の添加量は樹脂組成物１００重量部当たり０〜３００重量部、好ましくは１０〜２００重量部である。
この範囲の補強性充填剤を使用することにより、好ましい発泡性と機械的強度の向上を図ることが出来る。
また、本発明の樹脂組成物はその特性改良に各種の添加剤を添加できる。例えば、補強性無機充填剤とゴムを結合するようなシランカップリング剤などである。
【００４４】
シランカップリング剤としては例えば、テトラエトキシシラン、ビニルトリメトキシシラン、ビニルトリス（２−メトキシエトキシ）シラン、３−アミノプロピルトリエトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、ビス−〔３−（トリエトキシシリル）−プロピル〕テトラスルフィド、ビス−〔３−（トリエトキシシリル）−プロピル〕ジスルフィド、トリエトキシシリルプロピル−メタクリレート−モノスルフィドなどであり、好ましい使用量は樹脂組成物１００重量部に対し０．５〜２０重量部、より好ましくは１〜１０重量部であり２種以上を併用しても良い。
【００４５】
本発明の樹脂組成物は分散剤や活性剤として例えば、ステアリン酸、オレイン酸、ラウリン酸などの脂肪酸やその誘導体またはジエチレングリコールやポリエチレングリコールなどを樹脂組成物１００重量部に対して１０重量部以下添加しても良い。
その他、非汚染性の老化防止剤、酸化防止剤、オゾン劣化防止剤、紫外線吸収剤などの各種安定剤や用途に応じて顔料などの着色剤を添加しても良い。
【００４６】
本発明の樹脂組成物は、分子量１００，０００〜１，２００，０００の官能基変性ジエン系重合体２〜５０重量部と酢酸ビニル含有量６〜４５重量％のエチレン酢酸ビニルコポリマー（ＥＶＡ）９８〜５０重量部及び上記のような架橋剤、発泡剤その他の添加剤を必要量混合して、発泡・架橋成形するものである。混合方法は公知の各種方法が使用できる。例えば混練機を使用して混合する方法であり、混練機としては例えばバンバリーミキサー、加圧ニーダー、インターミキサー、押出し機、オープンロールなどが挙げられる。
【００４７】
原料の混合工程は特に制限は無いが再練時に発泡剤、架橋剤などその他添加剤を添加しても良い。混練温度は５０〜１２０℃程度が推奨される。混練機などで各種原料を混練混合して得られた未架橋の配合組成物はインジェクション成型機で必要量金型に装填され、発泡架橋される。又は加熱プレスなどで、発泡架橋成形し本発明の発泡弾性体が得られる。
発泡・架橋は２段階以上に渡って実施することも、連続的に実施することも可能である。発泡、架橋温度は１２０〜２２０℃、好ましくは１３０〜２００℃である。
【００４８】
本発明の樹脂組成物の製造に使用する原料重合体及び各種充填剤中の水分などの揮発分はできるだけ少ないほうが好ましい。揮発分が多い原料重合体や充填剤を使用する場合は出来れば予め乾燥して使用することが望ましい。しかし、１００℃以上の高温練によって混練と同時に揮発分を蒸発除去する事も可能である。配合物に水分などの揮発分が残っていると、製造した架橋発泡弾性体の架橋・加硫が不均質になり、充分な物性が得られない。
【００４９】
本発明の樹脂組成物は艶消し効果と加熱収縮性が優れるので質感や寸法安定性が要求されるあらゆる用途に利用できる。特にアウトソールやミッドソールなどの各種履物用途に有用であり、その他例えば、緩衝材、ソリッドタイヤ、自動車用品、ＯＡ機器や事務用品、家電、医療用途、スポーツ用品、玩具、家具など各種用途に使用できる。
【００５０】
【実施例】
以下、実施例によって本発明を説明するが、本発明の技術的範囲はこれら実施例に限定されるものではない。
【００５１】
〔参考例〕実施例で使用した原料ジエン系重合体の調製
バッチ重合によるシクロヘキサン溶媒中、ｎ−ブチルリチウムを重合開始剤としてスチレンモノマーと１，３−ブタジエンを共重合し、スチレン・ブタジエンゴムＳＢＲ−Ａ〜Ｅを製造した。
【００５２】
（ＳＢＲ−ＡとＳＢＲ−Ｂの製造）
窒素置換した攪拌機付き１０Ｌオートクレーブに脱水シクロヘキサン溶媒５．５ｋｇとスチレンモノマー０．４５ｋｇ及び１，３−ブタジエン０．４０ｋｇを装填した。攪拌しながら温度を６０℃まで昇温してテトラヒドロフラン３２ｇとｎ−ブチルリチウム０．６３ｇ（１５％シクロヘキサン溶液）を添加して重合反応を開始した。重合の途中から最高温度の９２℃になるまでの５分間１，３−ブタジエン０．１５ｋｇを重合系中に連続して添加した。
重合の最高温度から３分後に重合体溶液の１／２量を抜き出しｎ−ブチルリチウムの１０倍モルの水で失活してＳＢＲ−Ａを得た。
オートクレーブ中の活性重合体に、重合開始剤として使用したｎ−ブチルリチウムに対して、その１／４モル量（オートクレーブ中の重合体のリチウムに対して１／２モル量）のテトラグリシジル−１，３−ビスアミノメチルシクロヘキサンを添加して反応し、ＳＢＲ−Ｂを得た。
【００５３】
（ＳＢＲ−ＣとＳＢＲ−Ｄの製造）
窒素置換した攪拌機付き１０Ｌオートクレーブに脱水シクロヘキサン溶媒５．４ｋｇとスチレンモノマー０．３５ｋｇ及び１，３−ブタジエン０．６５ｋｇを装填した。攪拌しながら温度を５４℃まで昇温してテトラヒドロフラン２２ｇとｎ−ブチルリチウム０．７６ｇ（１５％シクロヘキサン溶液）を添加して重合反応を開始した。最高温度が９１℃になり３分後に重合体溶液の１／２量を抜き出しｎ−ブチルリチウムの１０倍モルの水で失活してＳＢＲ−Ｃを得た。
オートクレーブ中の活性重合体に、重合開始剤として使用したｎ−ブチルリチウムに対して、１／２量（オートクレーブ中の重合体のリチウムに対して等モル量）の１，３−ジメチルイミダゾリジノンを添加して反応し、ＳＢＲ−Ｄを得た。
【００５４】
（ＳＢＲ−Ｅの製造）
窒素置換した攪拌機付き１０Ｌオートクレーブに脱水シクロヘキサン溶媒５．４ｋｇとスチレンモノマー０．３８ｋｇ及び１，３−ブタジエン０．６２ｋｇを装填した。攪拌しながら温度を４８℃まで昇温してテトラヒドロフラン３２ｇとｎ−ブチルリチウム０．９３ｇ（１５％シクロヘキサン溶液）を添加して重合反応を開始した。最高温度が８９℃になり３分後に重合体溶液を抜き出しｎ−ブチルリチウムの１０倍モルの水で失活してＳＢＲ−Ｅを得た。
ＳＢＲ−ＢとＳＢＲ−Ｄも反応終了後、オートクレーブから抜き出した後それぞれの重合体溶液に水をｎ−ブチルリチウムの１０倍モル量添加して反応を停止した。その後、各重合体溶液に夫々安定剤として２，６−ジ−ｔｅｒｔブチル−４−メチルフェノールをゴム１００重量部当たり０．５重量部添加し、ドラムドライヤーで脱溶媒、乾燥して仕上げた。
表１に製造したスチレン・ブタジエンゴムの分析値を記載した。
【００５５】
《調製スチレン・ブタジエンゴムの分析方法》
（１）結合スチレン量
紫外分光光度計（日本分光社製 Ｖ−５２０ ＵＶ）で、標準ポリスチレンのＵＶ吸収強度と比較して求めた。
（２）スチレンブロック量
ゴム状重合体２重量部をクロロホルム１００重量部に溶解し、ターシャリーブチルヒドロペルオキシド５重量部とオスミウムテトラオキシド０．０１重量部を添加した後、攪拌しながら８０℃湯浴中で１５分間分解した後、分解溶液に１０倍容量のメタノールを添加して生成沈澱物を濾別（フィルター網目サイズ０．４５μｍ）し、乾燥してその重量からゴム状重合体中のスチレンブロック量を求めた。
【００５６】
（３）ブタジエン中の１，２ビニル結合量
赤外分光光度計（日本分光社製 Ｖ−５２０ ＵＶ）で測定しハンプトン法で求めた。
（４）スチレン・ブタジエンゴムの分子量測定
東ソー社製ＧＰＣ（ゲルパーミエーション クロマトグラフィー）ＨＬＣ−８１２０ＧＰＣ型を使用し、東ソー社製スチレン系カラムＴＳＫｇｅｌ ＳｕｐｅｒＨＭ−Ｍ、展開溶媒はＴＨＦ（テトラヒドロフラン）を流量０．５ｍｌ／分、試料濃度５ｍｇ／５ｍｌＴＨＦ溶媒として測定した。
【００５７】
《実施例及び比較例発泡弾性体の調製》
配合混練は、ロール温度７０℃の６インチオープンロールを使用して表２に示す配合処方で混練した。
スチレン・ブタジエンゴムとＥＶＡをロールで混練混合し、架橋剤と発泡剤以外の原料を混合した後、室温で冷却した。
その後、再度ロールで架橋剤と発泡剤を添加して混合しゴム組成物を調整した。得られたゴム組成物を温度１６０℃、金型で発泡・架橋成形し発泡弾性体を得た。２３℃恒温室で一昼夜保存後、発泡弾性体の物性を測定した。発泡弾性体の物性測定結果を表３に記載した。
【００５８】
（実施例及び比較例発泡弾性体の物性測定方法）
・引張試験
ＪＩＳ Ｋ６２５１に準拠し、２３℃恒温室で測定した。
・引き裂き試験
ＪＩＳ Ｋ６２５２に準拠し、２３℃恒温室で測定した。
・硬度の測定
高分子計器（株）製 ＡＳＫＥＲ硬度計 型式Ｃを使用して、２３℃恒温室で測定した。
・比重
発泡・架橋成型した試料の重量を同試料の体積で除して算出した。
【００５９】
・加熱収縮性
発泡・架橋成型した試料を７０℃のオーブンに４０分間入れた後、取り出して２３℃室温で放冷し、その長辺の長さ収縮率を測定した。
・圧縮永久歪（ｃ−ｓｅｔ）
２５％圧縮、５０℃で６時間テストをした。
・光沢
村上色彩技術研究所製のディジタル光沢計ＧＭ−２６Ｄを使用して、ＪＩＳ Ｋ７１０５に準じて６０°光沢を測定した。
【００６０】
【表１】
【表２】
【表３】
【発明の効果】
本発明の樹脂組成物は、インジェクションや型物の架橋・成型で光沢度が抑えられ艶消し効果が極めて大きいので成形品の質感が向上する。艶消しして質感を向上する加工工程が不要になり、加工コストが低減され更に環境汚染がない。熱収縮性や機械的強度も優れているので、特にアウトソールやミッドソールなどの各種履物用素材として有用であり、また緩衝材や各種工業用品などにも利用できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a resin composition that suppresses gloss and has an excellent matting effect, a foamed product thereof, and footwear using the resin composition.
[0002]
[Prior art]
Conventionally, lightweight foamed shoe soles for shoe use, etc., are often made of ethylene vinyl acetate copolymer (hereinafter sometimes abbreviated as EVA) that has features such as foaming, rubber elasticity, flexibility, and low-temperature characteristics for weight reduction purposes. Has been. However, EVA foam has an unfavorable luster due to its high glossiness and poor texture.
In order to solve this problem, the foamed sheet is manufactured by a compression mold and then molded, but the material loss rate is very large. In addition, foam molding with an injection mold requires a matte prescription such as stone wash, but it is desired to solve various problems such as material loss and environmental measures.
Furthermore, the heat shrinkability of the foamed molded product is large, which is an obstacle to secondary vulcanization.
[0003]
Patent Document 1 discloses a foam composition composed of EVA and hydrogenated acrylonitrile butadiene rubber (HNBR), and discloses improving the wear resistance of EVA and the hardness of HNBR.
Patent Document 2 discloses that the foam composition of styrene-butadiene block copolymer and EVA or styrene-butadiene block copolymer and polyurethane (PU) has a small change in hardness due to temperature.
[0004]
[Patent Document 1]
JP 2002-34601 A
[Patent Document 2]
JP 2001-340105 A
[0005]
[Problems to be solved by the invention]
It is an object of the present invention to provide a resin composition that suppresses glossiness and has an extremely large matting effect and is excellent in heat shrinkability and mechanical strength, and footwear having an excellent texture using the resin composition. To do.
[0006]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present invention has found that a resin composition comprising a specific diene polymer and EVA has an extremely large matting effect while suppressing glossiness and is excellent in heat shrinkability and mechanical strength. It has been made.
[0007]
That is, the present invention
(1) 2 to 50 parts by weight of a diene polymer having a molecular weight of 100,000 to 1,200,000 modified with a functional group and an ethylene vinyl acetate copolymer (EVA) 98 to 50 having a vinyl acetate content of 6 to 45% by weight A resin composition comprising parts by weight,
(2) The resin composition according to the above (1), wherein the vinyl aromatic bond content of the diene polymer is 25 to 75% by weight,
(3) The resin composition according to the above (1) and (2), wherein the vinyl aromatic block bond amount of the diene polymer is 18% by weight or less,
[0008]
(4) The above (1), wherein the diene polymer is a functional group-modified diene polymer modified with at least one compound selected from nitrogen-containing compounds, oxygen-containing compounds, silicon-containing compounds, and tin-containing compounds. To the resin composition according to any one of (3),
(5) The above-mentioned (1) to (4), wherein the diene polymer is a functional group-modified diene polymer modified with a compound having at least one of amino group, amide group, imino group, epoxy group and silanol group. ) The resin composition according to any one of
(6) The resin composition according to any one of (1) to (5), wherein the diene polymer is a functional group-modified diene polymer modified with a compound represented by the following formula (1):
[0009]
[Chemical 2]
(7) A foamed elastic body using the resin composition according to any one of (1) to (6) above,
(8) Footwear using the resin composition according to any one of (1) to (6) or the foamed elastic body according to (7),
It is.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to 2 to 50 parts by weight of a diene polymer having a molecular weight of 100,000 to 1,200,000 modified with a functional group and an ethylene vinyl acetate copolymer (EVA) 98 to 98% having a vinyl acetate content of 6 to 45% by weight. It is a resin composition consisting of 50 parts by weight, and particularly has a favorable texture in which the glossiness of the resin composition is suppressed and is excellent in heat shrinkability.
[0012]
The diene polymer modified with a functional group used in the present invention is a main peak molecular weight in terms of polystyrene measured by gel permeation chromatography (hereinafter referred to as GPC) (if the chromatogram has a plurality of peaks, the peak The molecular weight of the highest portion is 100,000 to 1,200,000, preferably 300,000 to 1,100,000, more preferably 400,000 to 1,000,000. A resin composition having an excellent matting effect in this molecular weight range is obtained.
[0013]
The diene polymer modified with a functional group used in the present invention is a polymer having various functional groups in the molecule.
Examples of the diene polymer having various functional groups in the molecule include polybutadiene rubber (BR), styrene / butadiene rubber (SBR), polyisoprene rubber (IR), styrene / isoprene / butadiene rubber (SIBR), and nitrile / butadiene. Rubber (NBR) and modified rubber such as high purity natural rubber (NR).
[0014]
The functional group addition position in the functional group-modified diene polymer includes molecular terminal modification, molecular both terminal (head-to-tail) modification, coupling modification, main chain modification, and the like. Examples of the method for performing molecular terminal modification include a method of modifying a polymerized molecular active terminal with a functional group-containing compound.
For example, both ends may be modified by using a polyfunctional initiator as a catalyst for anionic polymerization to modify the active end of the polymer, or by using an initiator having a functional group to modify the active end of the polymer. These include a method of modifying the active terminal of the polymer using a group-containing monomer as a polymerization raw material, or a method of coupling the active terminal of a functional group-containing polymer with a coupling agent. A polymer modified by coupling by treating the active terminal of the polymer with a polyfunctional modifier can also be used as a preferred diene polymer.
[0015]
The functional group-modified diene-based polymer is 2 to 50 parts by weight, preferably 3 to 40 parts by weight in 100 parts by weight of the resin composition of the present invention. A small resin composition excellent in heat shrinkage is obtained.
A preferred functional group-modified diene polymer of the composition of the present invention has a vinyl aromatic bond content of 25 to 75% by weight, particularly preferably 30 to 70% by weight. In this range, a preferred heat-shrinkable resin composition is obtained. It is done.
In addition, it is desirable that the functional group-modified diene polymer of the composition of the present invention has a vinyl aromatic block bond amount of 18% by weight or less, and the vinyl aromatic bond bond is more random. By making the bond of vinyl aromatic more random, a preferable matting effect and compression set resistance can be obtained.
[0016]
A particularly preferred functional group-modified diene polymer of the present invention is a functional group-modified styrene-butadiene rubber.
The preferred bound styrene content of the functional group-modified styrene / butadiene rubber used in the present invention is 25 to 75% by weight, particularly preferably 30 to 70% by weight. More preferable matting effect can be obtained within the bound styrene content.
[0017]
As for the distribution of styrene in the molecule of the functional group-modified styrene / butadiene rubber, the random distribution has a higher matting effect. The amount of vinyl bonds in the butadiene portion of the functional group-modified polybutadiene rubber or functional group-modified styrene / butadiene rubber is not particularly limited, but when used for a shoe sole or the like, it is preferably 80% by weight or less in view of wear resistance.
The higher the functional group modification rate of the rubber composition of the present invention, the better the balance between the matte effect and the physical properties, and the proportion of the modified rubber to which one or more functional groups are added among all rubber molecules (modification rate). ) Is 20% by weight or more, preferably 40% by weight or more.
[0018]
The modifier compound of the functional group-modified rubbery polymer of the rubber composition of the present invention is preferably one or more of nitrogen-containing compounds, oxygen-containing compounds, silicon-containing compounds and tin-containing compounds. Examples of the nitrogen-containing compound include compounds having an amino group, an amide group, an imino group, and the like, such as dimethylamine, methylethylamine, diethylamine, diphenylamine, and N-methylaniline, and N-alkyl cyclic lactam compounds, N- An alkyl cyclic urea compound or an N-alkylbenzophenone compound is also a preferable functional group-containing compound. Specific examples of the compound include N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N, N'-dimethylbenzophenone and the like.
[0019]
Examples of the oxygen-containing compound include an epoxy group, a carboxyl group, and a hydroxyl group, and particularly preferred is a compound containing an epoxy group. Examples of the compound having an epoxy group include epoxidized soybean oil, epoxidized linseed oil, and epoxidized polybutadiene. A compound having a glycidyl group is also suitable.
Particularly preferred epoxy group-containing compounds are, for example, diglycidyl compounds represented by the following formula (1).
[0020]
[Chemical 3]
Specific examples of the compound represented by the formula (1) include polyglycidyl ethers of polyhydric alcohols such as ethylene glycol diglycidyl ether, 1,4-diglycidylbenzene, polyepoxy compounds such as polyepoxidized liquid polybutadiene, Epoxy group-containing tertiary amines such as 4,4′-diglycidyl-diphenylmethylamine, 4,4′-diglycidyl-dibenzylmethylamine, diglycidylaniline, diglycidylorthotoluidine, tetraglycidylmetaxylenediamine, diglycidylaminomethyl Examples thereof include diglycidylamino compounds such as cyclohexane and tetraglycidyl-1,3-bisaminomethylcyclohexane.
As the epoxy group-containing compound, for example, a compound represented by the following formula (2) is also a preferable compound.
[0022]
[Formula 4]
R in the formula (2) is a diepoxy compound represented by the formulas (3) to (5).
[0024]
[Chemical formula 5]
[Chemical 6]
Or
[0027]
[Chemical 7]
Specific examples include bisphenol A diglycidyl ether and bisphenol F diglycidyl ether represented by formula (6) or (7), and other alkylene oxide-containing epoxy compounds, alicyclic epoxy compounds, and carbocyclic compound-containing epoxy compounds. A mixture of the compounds represented by the formula (2) can also be used.
[0029]
[Chemical 8]
[Chemical 9]
(In the formula, n represents an integer of 0 to 10)
[0032]
Examples of the silicon-containing compound include compounds having a halogen or an alkoxy group, such as silicon tetrachloride, trichloromethylsilane, dichlorodimethylsilane, trimethylchlorosilane, tetramethoxysilane, tetraethoxysilane, and dibromodimethylsilane.
Examples of tin-containing compounds include tin halides, such as tin tetrachloride, tin dichloride, triphenyltin chloride, and tributyltin chloride.
[0033]
Further, both end-modified diene polymers are obtained by using, as a polymerization initiator, a polylithium compound obtained by modifying an organic alkali metal such as an organic lithium compound with a polyvinyl compound such as divinylbenzene or diisopropenylbenzene. The active terminal is modified with a functional group-containing compound. In addition, for example, the active terminal of a polymer obtained by using a functional group-containing polymerization initiator such as an amide lithium compound is coupled with a coupling agent or modified with a functional group-containing compound. Furthermore, a functional group-containing monomer such as an amino group-containing compound such as N, N-dimethylaminomethylstyrene, N, N-diethylaminomethylstyrene, N, N-dimethylaminoethylstyrene was obtained as a polymerization raw material. These include a method for modifying the active terminal of the polymer and a method for coupling.
[0034]
Two or more such functional group-containing modifiers can be used in combination, and other modifiers can be used. A modifier and a coupling agent can be used in combination. The functional group-modified diene polymer used in the present invention may have a linear structure or a branched structure.
The functional group-modified diene polymer used in the present invention is preferably a solution-polymerized rubber with few impurities that have excellent colorability when used in transparent products and color applications.
[0035]
The ethylene-vinyl acetate copolymer (EVA) used in the present invention includes various commercial products depending on the vinyl acetate content, but those having a vinyl acetate content of 6 to 45% by weight can be used. The preferred vinyl acetate content range is 8-40% by weight. In this range, it has good processability, and by blending the functional group-modified diene polymer, the matte effect and the physical property balance become good.
[0036]
The present invention relates to a resin composition comprising 2 to 50 parts by weight of a diene polymer having a molecular weight of 100,000 to 1,200,000 and 98 to 50 parts by weight of an ethylene vinyl acetate copolymer (EVA) having a vinyl acetate content of 6 to 45% by weight. In addition, it is composed of a foaming agent, a crosslinking agent, and various additives. Further, other polymers may be mixed with 50% by weight or less of EVA if necessary.
Examples of other diene polymers include natural rubber (NR), polyisoprene rubber (IR), polybutadiene rubber (BR), styrene / butadiene rubber (SBR), acrylonitrile rubber (NBR), and ethylene / propylene rubber (EPM). Or EPDM).
[0037]
A well-known thing is used as a foaming agent used by this invention. For example, one or more of sodium carbonate, ammonium carbonate, sodium bicarbonate, ammonium bicarbonate, azodicarbonamide, N, N′-dinitrosopentamethylenetetramine, azobisisobutyronitrile, benzenesulfonyl hydrazide and the like can be used. The amount of the foaming agent used is 1 to 25 parts by weight, preferably 2 to 20 parts by weight per 100 parts by weight of the resin composition, and preferable weight reduction and strength when the resin composition is used for a shoe sole or the like within this range. A performance balance such as The preferred specific gravity for weight reduction by foaming is 0.1 to 0.9, more preferably 0.15 to 0.7.
Moreover, organic acids such as salicylic acid, urea, or urea derivatives can be used as a foaming aid together with the foaming agent.
[0038]
Various known methods can be adopted as a method for crosslinking the foamed elastic body of the present invention. When a crosslinking agent is used, for example, an organic peroxide or a sulfur-based crosslinking agent / vulcanizing agent can be used. Examples of organic peroxides include dicumyl peroxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, cyclohexane peroxide, t-butylperoxybenzoate, and t-butylcumyl oxide. Benzoyl peroxide, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) octane, di-t-butyl peroxide and the like.
[0039]
In addition, sulfur or various treated sulfur and sulfur derivatives can be used as the sulfur-based vulcanizing agent. For example, 4-4'-dithiodimorpholine. In addition, p-quinone dioxime, p-p'-dibenzoylquinone dioxime, N, N'-m-phenylene dimaleimide and the like can also be used. When such a vulcanizing agent is used, it is effective to use a vulcanization accelerator in combination.
[0040]
Examples of the vulcanization accelerator include aldehyde ammonia, aldehyde amine, thiourea, guanidine, thiazole, aldehyde amine, sulfenamide, thiuram, and dithiocarbamate. Hexamethylenetetramine, n-butyraldehyde aniline, N, N'-diphenylthiourea, 1,3-diphenylguanidine, di-o-tolylguanidine, 2-mercaptobenzothiazole, dibenzothiazolyl disulfide, n-cyclohexyl-2 -Benzothiazolylsulfenamide, N-tert-butyl-2-benzothiazolylsulfenamide, tetramethylthiuram disulfide, tetrakis (2-ethylhexyl) thiuram disulfide, dipentamethylenethiuram tetrasulfide Zinc dimethyl dithiocarbamate and the like.
[0041]
In the resin composition of the present invention, various rubber extending oils may be added as a softening agent within the range of the object of the present invention in an amount of 0 to 100 parts by weight per 100 parts by weight of the total polymer.
Examples of oils that can be added include mineral oils such as aroma oils, paraffin oils, and naphthenic oils, and animal and plant oils such as soybean oil and linseed oil, and a mixture of two or more of these may be used. A preferred extending oil is a non-contaminating mineral oil in consideration of the colorability of the resin composition, for example, naphthenic oil or paraffin oil.
[0042]
The resin composition of the present invention can use various fillers as necessary. Generally known as a filler for resin and rubber, such as carbon black, silica, zinc white, zinc carbonate, calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium carbonate, magnesium carbonate, clay, talc, mica, etc. Preferred are hard clay, calcium carbonate, silica and the like, and two or more kinds can be used in combination. A filler having a reinforcing effect is desirable.
[0043]
The addition amount of the filler is 0 to 300 parts by weight, preferably 10 to 200 parts by weight, per 100 parts by weight of the resin composition.
By using the reinforcing filler in this range, it is possible to improve the preferable foamability and mechanical strength.
Moreover, the resin composition of this invention can add various additives for the characteristic improvement. For example, a silane coupling agent that binds a reinforcing inorganic filler and rubber.
[0044]
Examples of the silane coupling agent include tetraethoxysilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, bis- [3- ( Triethoxysilyl) -propyl] tetrasulfide, bis- [3- (triethoxysilyl) -propyl] disulfide, triethoxysilylpropyl-methacrylate-monosulfide, and the like. The preferred amount used is 100 parts by weight of the resin composition. It is 0.5-20 weight part, More preferably, it is 1-10 weight part, and may use 2 or more types together.
[0045]
In the resin composition of the present invention, for example, a fatty acid such as stearic acid, oleic acid or lauric acid or a derivative thereof or diethylene glycol or polyethylene glycol is added as a dispersant or an activator in an amount of 10 parts by weight or less based on 100 parts by weight of the resin composition. You may do it.
In addition, various stabilizers such as non-polluting anti-aging agents, antioxidants, ozone deterioration inhibitors, ultraviolet absorbers, and coloring agents such as pigments may be added according to applications.
[0046]
The resin composition of the present invention comprises an ethylene vinyl acetate copolymer (EVA) 98 having 2 to 50 parts by weight of a functional group-modified diene polymer having a molecular weight of 100,000 to 1,200,000 and a vinyl acetate content of 6 to 45% by weight. -50 parts by weight and the above-mentioned cross-linking agent, foaming agent and other additives are mixed in a necessary amount to perform foaming and cross-linking molding. Various known methods can be used as the mixing method. For example, it is a method of mixing using a kneader, and examples of the kneader include a Banbury mixer, a pressure kneader, an intermixer, an extruder, and an open roll.
[0047]
The raw material mixing step is not particularly limited, but other additives such as a foaming agent and a crosslinking agent may be added during re-milling. A kneading temperature of about 50 to 120 ° C. is recommended. An uncrosslinked blended composition obtained by kneading and mixing various raw materials with a kneader or the like is charged into a necessary amount of a mold with an injection molding machine and foamed and crosslinked. Alternatively, the foamed elastic body of the present invention can be obtained by foaming and crosslinking with a hot press or the like.
Foaming / crosslinking can be carried out in two or more stages or continuously. The foaming and crosslinking temperature is 120 to 220 ° C, preferably 130 to 200 ° C.
[0048]
It is preferable that the raw material polymer and various fillers used in the production of the resin composition of the present invention have as little volatile components as possible. When using a raw material polymer or filler with a large amount of volatile matter, it is desirable to dry it before use. However, it is also possible to evaporate and remove volatile components simultaneously with kneading by high temperature kneading at 100 ° C. or higher. If volatile components such as moisture remain in the blend, the produced crosslinked foamed elastic body will be heterogeneous in crosslinking and vulcanization, and sufficient physical properties will not be obtained.
[0049]
Since the resin composition of the present invention has an excellent matting effect and heat shrinkability, it can be used in any application where texture and dimensional stability are required. It is especially useful for various footwear applications such as outsole and midsole. For example, it is used for various applications such as cushioning materials, solid tires, automobile supplies, office automation equipment, office supplies, home appliances, medical applications, sports equipment, toys, furniture, etc. it can.
[0050]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention, the technical scope of this invention is not limited to these Examples.
[0051]
[Reference Example] Preparation of raw material diene polymer used in Examples
In a cyclohexane solvent by batch polymerization, styrene monomer and 1,3-butadiene were copolymerized using n-butyllithium as a polymerization initiator to produce styrene-butadiene rubbers SBR-AE.
[0052]
(Production of SBR-A and SBR-B)
A 10-liter autoclave equipped with a stirrer substituted with nitrogen was charged with 5.5 kg of dehydrated cyclohexane solvent, 0.45 kg of styrene monomer, and 0.40 kg of 1,3-butadiene. The temperature was raised to 60 ° C. while stirring, and 32 g of tetrahydrofuran and 0.63 g of n-butyllithium (15% cyclohexane solution) were added to initiate the polymerization reaction. 0.15 kg of 1,3-butadiene was continuously added to the polymerization system for 5 minutes from the middle of the polymerization to the maximum temperature of 92 ° C.
Three minutes after the maximum temperature of the polymerization, ½ amount of the polymer solution was extracted and deactivated with 10 moles of water of n-butyllithium to obtain SBR-A.
For the active polymer in the autoclave, ¼ mole amount of tetraglycidyl-1 (1/2 mole amount relative to lithium of the polymer in the autoclave) with respect to n-butyllithium used as a polymerization initiator. , 3-Bisaminomethylcyclohexane was added and reacted to obtain SBR-B.
[0053]
(Production of SBR-C and SBR-D)
A 10-liter autoclave equipped with a stirrer substituted with nitrogen was charged with 5.4 kg of dehydrated cyclohexane solvent, 0.35 kg of styrene monomer and 0.65 kg of 1,3-butadiene. The temperature was raised to 54 ° C. while stirring, and 22 g of tetrahydrofuran and 0.76 g of n-butyllithium (15% cyclohexane solution) were added to initiate the polymerization reaction. Three minutes after the maximum temperature reached 91 ° C., ½ amount of the polymer solution was extracted and deactivated with 10-fold mol water of n-butyllithium to obtain SBR-C.
1,3-dimethylimidazolidinone in 1/2 amount (equal molar amount with respect to lithium of the polymer in the autoclave) with respect to n-butyllithium used as the polymerization initiator in the active polymer in the autoclave To give SBR-D.
[0054]
(Manufacture of SBR-E)
A 10 L autoclave equipped with a stirrer purged with nitrogen was charged with 5.4 kg of dehydrated cyclohexane solvent, 0.38 kg of styrene monomer and 0.62 kg of 1,3-butadiene. The temperature was raised to 48 ° C. while stirring, and 32 g of tetrahydrofuran and 0.93 g of n-butyllithium (15% cyclohexane solution) were added to initiate the polymerization reaction. Three minutes after the maximum temperature reached 89 ° C., the polymer solution was taken out and deactivated with 10-fold mol water of n-butyllithium to obtain SBR-E.
SBR-B and SBR-D were also extracted from the autoclave after the reaction was completed, and then the reaction was stopped by adding 10 times the molar amount of n-butyllithium to each polymer solution. Thereafter, 0.5 parts by weight of 2,6-di-tertbutyl-4-methylphenol as a stabilizer was added to each polymer solution per 100 parts by weight of rubber, and the solvent was removed with a drum dryer and dried.
Table 1 shows the analytical values of the styrene-butadiene rubber produced.
[0055]
<< Analytical Method of Prepared Styrene-Butadiene Rubber >>
(1) Bonded styrene content
It calculated | required with the ultraviolet spectrophotometer (JASCO Corporation V-520 UV) compared with the UV absorption intensity of standard polystyrene.
(2) Styrene block amount
2 parts by weight of a rubbery polymer is dissolved in 100 parts by weight of chloroform, 5 parts by weight of tertiary butyl hydroperoxide and 0.01 parts by weight of osmium tetraoxide are added, and then decomposed in an 80 ° C. water bath for 15 minutes with stirring. After that, 10-fold volume of methanol was added to the decomposition solution, and the resulting precipitate was separated by filtration (filter network size 0.45 μm), dried, and the amount of styrene block in the rubber-like polymer was determined from its weight.
[0056]
(3) 1,2-vinyl bond amount in butadiene
It measured with the infrared spectrophotometer (JASCO Corporation V-520 UV), and calculated | required with the Hampton method.
(4) Molecular weight measurement of styrene-butadiene rubber
Tosoh GPC (gel permeation chromatography) HLC-8120GPC type is used, Tosoh styrene column TSKgel SuperHM-M, developing solvent THF (tetrahydrofuran) flow rate 0.5ml / min, sample concentration 5mg / 5mlTHF. Measured as solvent.
[0057]
<< Preparation of Examples and Comparative Examples Foamed Elastic Body >>
The compounding kneading was performed using the 6-inch open roll with a roll temperature of 70 ° C. according to the formulation shown in Table 2.
Styrene-butadiene rubber and EVA were kneaded and mixed with a roll, and raw materials other than the crosslinking agent and foaming agent were mixed, and then cooled at room temperature.
Then, the rubber composition was prepared by adding and mixing the crosslinking agent and the foaming agent again with a roll. The obtained rubber composition was foamed and cross-linked with a mold at a temperature of 160 ° C. to obtain a foamed elastic body. After storage for one day in a 23 ° C. constant temperature room, the physical properties of the foamed elastic body were measured. The physical property measurement results of the foamed elastic body are shown in Table 3.
[0058]
(Methods for measuring physical properties of foamed elastic bodies of Examples and Comparative Examples)
・ Tensile test
Based on JIS K6251, it measured in a 23 degreeC constant temperature room.
・ Tear test
Based on JIS K6252, it measured in a 23 degreeC thermostatic chamber.
・ Measurement of hardness
Using an ASKER hardness meter Model C manufactured by Kobunshi Keiki Co., Ltd., measurement was performed at 23 ° C. in a constant temperature room.
·specific gravity
The weight was calculated by dividing the weight of the foamed / crosslinked sample by the volume of the sample.
[0059]
・ Heat shrinkage
The foamed / crosslinked molded sample was placed in an oven at 70 ° C. for 40 minutes, then taken out and allowed to cool at room temperature at 23 ° C., and the length shrinkage of the long side was measured.
・ Compression set (c-set)
Tested at 25% compression, 50 ° C. for 6 hours.
・ Glossy
Using a digital gloss meter GM-26D manufactured by Murakami Color Research Laboratory, 60 ° gloss was measured according to JIS K7105.
[0060]
[Table 1]
[Table 2]
[Table 3]
【The invention's effect】
The resin composition of the present invention has a reduced glossiness by injection and crosslinking / molding of the mold, and has a very large matting effect, so that the texture of the molded product is improved. A processing step for matting to improve the texture becomes unnecessary, processing costs are reduced, and there is no environmental pollution. Since it has excellent heat shrinkability and mechanical strength, it is particularly useful as a material for various footwear such as outsole and midsole, and can also be used for cushioning materials and various industrial products.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003193491A JP4789403B2 (en) | 2003-07-08 | 2003-07-08 | Resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003193491A JP4789403B2 (en) | 2003-07-08 | 2003-07-08 | Resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005029609A true JP2005029609A (en) | 2005-02-03 |
| JP4789403B2 JP4789403B2 (en) | 2011-10-12 |
Family
ID=34204942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003193491A Expired - Fee Related JP4789403B2 (en) | 2003-07-08 | 2003-07-08 | Resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4789403B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009024144A (en) * | 2007-07-24 | 2009-02-05 | Tosoh Corp | Ethylene-vinyl acetate copolymer composition |
| JP2014189773A (en) * | 2013-03-28 | 2014-10-06 | Asahi Kasei Chemicals Corp | Ethylene-vinyl acetate copolymer resin composition, crosslinked foam, and footwear |
| KR20170074676A (en) * | 2015-12-22 | 2017-06-30 | 주식회사 엘지화학 | Modifying agent, preparation method of modified conjugated diene polymer using the modifying agent and modified conjugated diene polymer |
| JP2019188123A (en) * | 2018-04-20 | 2019-10-31 | ナノテック セラミックス カンパニー リミテッドＮａｎｏｔｅｃｈ Ｃｅｒａｍｉｃｓ Ｃｏ．， Ｌｔｄ． | Composition for manufacturing lightweight footwear having improved heat-resistance and lightweight footwear manufactured using the same |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5513727A (en) * | 1978-07-17 | 1980-01-30 | Asahi Chem Ind Co Ltd | Adhesive composition |
| WO1987005610A1 (en) * | 1986-03-13 | 1987-09-24 | Asahi Kasei Kogyo Kabushiki Kaisha | Diene polymers, process for their preparation, and rubber composition containing them |
| JPH01101357A (en) * | 1987-10-14 | 1989-04-19 | Asahi Chem Ind Co Ltd | Block copolymer composition |
| JPH0543770A (en) * | 1991-08-09 | 1993-02-23 | Japan Synthetic Rubber Co Ltd | Thermoplastic elastomer composition |
| JPH11335433A (en) * | 1998-05-22 | 1999-12-07 | Nippon Elastomer Kk | New rubbery polymer, its production and resin composition of the same |
| JP2000014404A (en) * | 1998-06-27 | 2000-01-18 | Moon Star Co | Antistatic shoes sole material |
| JP2001197902A (en) * | 2000-01-18 | 2001-07-24 | Jsr Corp | Sole member for footware |
| JP2001340105A (en) * | 2000-06-01 | 2001-12-11 | Asics Corp | Foam for midsole or inner sole of shoes |
| JP2002034601A (en) * | 2000-07-27 | 2002-02-05 | Asics Corp | Foamed body for light outsole of shoes |
| JP2002201333A (en) * | 2000-10-30 | 2002-07-19 | Asahi Kasei Corp | Block copolymer composition |
| JP2002284814A (en) * | 2001-03-26 | 2002-10-03 | Asahi Kasei Corp | Production method for modified conjugated diene polymer |
| JP2003012886A (en) * | 2001-06-28 | 2003-01-15 | Jsr Corp | Hydrogenated dienic polymer composition and molding |
| JP2003246911A (en) * | 2002-02-26 | 2003-09-05 | Asahi Kasei Corp | High-frequency fusible composition |
| JP2003246910A (en) * | 2002-02-26 | 2003-09-05 | Asahi Kasei Corp | Slush-molding material |
-
2003
- 2003-07-08 JP JP2003193491A patent/JP4789403B2/en not_active Expired - Fee Related
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5513727A (en) * | 1978-07-17 | 1980-01-30 | Asahi Chem Ind Co Ltd | Adhesive composition |
| WO1987005610A1 (en) * | 1986-03-13 | 1987-09-24 | Asahi Kasei Kogyo Kabushiki Kaisha | Diene polymers, process for their preparation, and rubber composition containing them |
| JPH09136993A (en) * | 1986-03-13 | 1997-05-27 | Asahi Chem Ind Co Ltd | Diene rubber composition |
| JPH01101357A (en) * | 1987-10-14 | 1989-04-19 | Asahi Chem Ind Co Ltd | Block copolymer composition |
| JPH0543770A (en) * | 1991-08-09 | 1993-02-23 | Japan Synthetic Rubber Co Ltd | Thermoplastic elastomer composition |
| JPH11335433A (en) * | 1998-05-22 | 1999-12-07 | Nippon Elastomer Kk | New rubbery polymer, its production and resin composition of the same |
| JP2000014404A (en) * | 1998-06-27 | 2000-01-18 | Moon Star Co | Antistatic shoes sole material |
| JP2001197902A (en) * | 2000-01-18 | 2001-07-24 | Jsr Corp | Sole member for footware |
| JP2001340105A (en) * | 2000-06-01 | 2001-12-11 | Asics Corp | Foam for midsole or inner sole of shoes |
| JP2002034601A (en) * | 2000-07-27 | 2002-02-05 | Asics Corp | Foamed body for light outsole of shoes |
| JP2002201333A (en) * | 2000-10-30 | 2002-07-19 | Asahi Kasei Corp | Block copolymer composition |
| JP2002284814A (en) * | 2001-03-26 | 2002-10-03 | Asahi Kasei Corp | Production method for modified conjugated diene polymer |
| JP2003012886A (en) * | 2001-06-28 | 2003-01-15 | Jsr Corp | Hydrogenated dienic polymer composition and molding |
| JP2003246911A (en) * | 2002-02-26 | 2003-09-05 | Asahi Kasei Corp | High-frequency fusible composition |
| JP2003246910A (en) * | 2002-02-26 | 2003-09-05 | Asahi Kasei Corp | Slush-molding material |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009024144A (en) * | 2007-07-24 | 2009-02-05 | Tosoh Corp | Ethylene-vinyl acetate copolymer composition |
| JP2014189773A (en) * | 2013-03-28 | 2014-10-06 | Asahi Kasei Chemicals Corp | Ethylene-vinyl acetate copolymer resin composition, crosslinked foam, and footwear |
| KR20170074676A (en) * | 2015-12-22 | 2017-06-30 | 주식회사 엘지화학 | Modifying agent, preparation method of modified conjugated diene polymer using the modifying agent and modified conjugated diene polymer |
| KR102019840B1 (en) * | 2015-12-22 | 2019-09-10 | 주식회사 엘지화학 | Modifying agent, preparation method of modified conjugated diene polymer using the modifying agent and modified conjugated diene polymer |
| JP2019188123A (en) * | 2018-04-20 | 2019-10-31 | ナノテック セラミックス カンパニー リミテッドＮａｎｏｔｅｃｈ Ｃｅｒａｍｉｃｓ Ｃｏ．， Ｌｔｄ． | Composition for manufacturing lightweight footwear having improved heat-resistance and lightweight footwear manufactured using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4789403B2 (en) | 2011-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1310987C (en) | Oil-extended rubber and rubber composition | |
| JP4259600B2 (en) | Thermoplastic elastomer composition, foam and method for producing the same | |
| WO2005085343A1 (en) | Rubber composition | |
| JP4130127B2 (en) | Modified rubber and production method and composition thereof | |
| JP5484005B2 (en) | Rubber composition | |
| JP4977939B2 (en) | Rubber composition and method for producing the same | |
| WO2014136458A1 (en) | Process for producing modified polymer, and rubber composition | |
| JP2006282964A (en) | Rubber composition | |
| JP5502473B2 (en) | Rubber composition for footwear | |
| JP2014210870A (en) | Rubber composition for tire tread and pneumatic tire using the same | |
| CN113924334A (en) | Silane coupling agent composition comprising silane compound and protein denaturing agent, and rubber composition comprising same | |
| KR20170076575A (en) | Polymer compound, preparation method of modified conjugated diene polymer using the polymer compound and modified conjugated diene polymer | |
| JP4789403B2 (en) | Resin composition | |
| JP5153071B2 (en) | Polymer foam containing hydrogenated copolymer | |
| JP2002220491A (en) | Production method of rubber composition for tire | |
| JP2014024912A (en) | Tread rubber composition for high-performance tire, and high-performance tire | |
| JP2008144044A (en) | Rubber composition for tire | |
| CN113490606A (en) | Sulfur-containing silane compounds and compositions thereof | |
| JP2011225651A (en) | Master batch for rubber composition and rubber composition using the master batch | |
| JP7081651B2 (en) | Rubber composition for tires | |
| TWI637025B (en) | Thermoplastic vulcanizate composition, method of forming the same and product thereof | |
| JP4687056B2 (en) | Method for producing reinforcing particles, polymer composition, method for producing the same, and vulcanizable rubber composition | |
| JP2004043627A (en) | Rubber composition and manufacturing process | |
| JP2015067827A (en) | Rubber composition and pneumatic tire using the same | |
| WO2024071407A1 (en) | Silane compound and composition containing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060706 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20081110 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20081209 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090206 |
|
| RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20090206 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100216 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100416 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110405 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110509 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110712 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110719 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140729 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |